NO138064B - PROCEDURES FOR THE PRODUCTION OF IMPACT-RESISTANT, WEATHER-RESISTANT POLYMERISATES OF VINYL CHLORIDE - Google Patents
PROCEDURES FOR THE PRODUCTION OF IMPACT-RESISTANT, WEATHER-RESISTANT POLYMERISATES OF VINYL CHLORIDE Download PDFInfo
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- NO138064B NO138064B NO2682/71A NO268271A NO138064B NO 138064 B NO138064 B NO 138064B NO 2682/71 A NO2682/71 A NO 2682/71A NO 268271 A NO268271 A NO 268271A NO 138064 B NO138064 B NO 138064B
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- Prior art keywords
- vinyl chloride
- ethylhexyl acrylate
- particle diameter
- weight
- resistant
- Prior art date
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 37
- 238000000034 method Methods 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 35
- 229920000058 polyacrylate Polymers 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 12
- 239000003995 emulsifying agent Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000005639 Lauric acid Substances 0.000 description 6
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 3
- 229940082004 sodium laurate Drugs 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 235000021313 oleic acid Nutrition 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 2
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- -1 tridecyl ester Chemical class 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Description
Den foreliggende oppfinnelse angår en fremgangsmåte for fremstilling av slagfaste,. forvitringsbestandige polymerisater av vinylklorid med K-verdier fra 60-75 ved emulsjonspolymerisasjon av vinylklorid i nærvær av forut-dannede polyakrylatdispersjoner. The present invention relates to a method for producing impact-resistant,. weathering-resistant polymers of vinyl chloride with K values from 60-75 by emulsion polymerization of vinyl chloride in the presence of preformed polyacrylate dispersions.
Det er kjent flere fremgangsmåter for fremstilling av slagfast polyvinylklorid. I folge det amerikanske patentskrift nr. 3.019.208 blir vinylklorid etter en emulsjonspolymerisasjons-fremgangsmåte podet med polyakrylsyreester med 1-10 karbonatomer i alkohol-resten under anvendelse av vannloselige katalysatorer, idet det anvendes i mengder fra 10 - 50 vektprosent av polyakrylater, Several methods are known for producing impact-resistant polyvinyl chloride. According to US Patent No. 3,019,208, vinyl chloride is grafted with polyacrylic acid esters with 1-10 carbon atoms in the alcohol residue by an emulsion polymerization method using water-soluble catalysts, using amounts from 10 to 50 percent by weight of polyacrylates,
for å oppnå en slagfasthet-forbedring. Ulempen ved å anvende så store mengder av lavere polyakrylater ligger i senkningen av mykningspunktet. For å unngå denne ulempe blir emulsjonspoly-merisasjonenav vinylklorid i folge det tyske utlegningsskrift nr. 1.206.589 gjennomfort i nærvær av en emulsjon av polyakryl-syretridecylester, idet det også kan anvendes små mengder. to achieve an impact resistance improvement. The disadvantage of using such large quantities of lower polyacrylates lies in the lowering of the softening point. In order to avoid this disadvantage, the emulsion polymerization of vinyl chloride is carried out in the presence of an emulsion of polyacrylic acid tridecyl ester according to German specification No. 1,206,589, as small amounts can also be used.
Den foreliggende oppfinnelse har til hensikt å fremstille en slagfast, forvitringsbestandig polyvinylklorid. The present invention aims to produce an impact-resistant, weathering-resistant polyvinyl chloride.
Oppfinnelsen angår folgelig en fremgangsmåte for fremstilling av slagfaste, forvitringsbestandige polymerisater av vinylklorid ved emulsjonspolymerisasjon av vinylklorid i nærvær av en vandig polyakrylatdispersjon, idet polyakrylatet er tilstede i en mindre mengde regnet på sluttproduktenes faststoffinnhold, The invention therefore relates to a method for the production of impact-resistant, weathering-resistant polymers of vinyl chloride by emulsion polymerization of vinyl chloride in the presence of an aqueous polyacrylate dispersion, the polyacrylate being present in a smaller amount based on the solids content of the final products,
og det særegne ved fremgangsmåten i henhold til oppfinnelsen er at vinylklorid polymeriseres i nærvær av 2 til 10 vektprosent fortrinnsvis 4 til 9 vektprosent av et polymerisat eller kopolymerisat av 2-etylheksylakrylat med minst 50 vektprosent 2-etylheksylakrylat, slik at polymerisasjonen av vinylklorid gjennomføres ved en temperatur fra 50 til 65°C og under god omrøring, i det minste så lenge ved metningstrykket for vinylklorid i nærvær av flytende vinylklorid, at omsetningen er 70%, idet den midlere partikkeldiameter av det anvendte polymerisat av 2-etylheksylakrylat ligger mellom følgende vexdier: maksimal midlere partikkeldiameter i nyu = 310 - (24.ganger polymerkonsentrasjonen av 2-etylheksylakrylat i vektprosent) og and the distinctive feature of the method according to the invention is that vinyl chloride is polymerized in the presence of 2 to 10 percent by weight, preferably 4 to 9 percent by weight, of a polymer or copolymer of 2-ethylhexyl acrylate with at least 50 percent by weight of 2-ethylhexyl acrylate, so that the polymerization of vinyl chloride is carried out at a temperature from 50 to 65°C and with good stirring, at least as long at the saturation pressure for vinyl chloride in the presence of liquid vinyl chloride, that the conversion is 70%, the mean particle diameter of the polymerized 2-ethylhexyl acrylate being used is between the following values: maximum mean particle diameter in nyu = 310 - (24 times the polymer concentration of 2-ethylhexyl acrylate in weight percent) and
minimal midlere partikkeldiameter i nya = 33 - (3,5 ganger polymerkonsentrasjonen av 2-etylheksylakrylat i vektprosent). minimum mean particle diameter in nya = 33 - (3.5 times the polymer concentration of 2-ethylhexyl acrylate in weight percent).
Disse og andre trekk ved fremgangsmåten i henhold til oppfinnelsen fremgår av patentkravene. These and other features of the method according to the invention appear in the patent claims.
Fortrinnsvis anvendes midlere partikkeldiametere, som ligger mellom følgende verdier: en maksimal midlere partikkeldiameter i mu = 260 - (24 ganger polymer-konsentrasjon av 2-etylheksylakrylat i vektprosent) og en minimal midlere partikkeldiameter i mp. = 33 - Preferably, average particle diameters are used, which lie between the following values: a maximum average particle diameter in mu = 260 - (24 times the polymer concentration of 2-ethylhexyl acrylate in weight percent) and a minimum average particle diameter in mp. = 33 -
(3,5 ganger polymer-konsentrasjon av 2-etylheksylakrylat i vektprosent) . Når man er i det angitte område blir det oppnådd polymerisater som ikke bare utmerker seg ved en god snittslagseighet, men også ved gjennomsiktighet. Generelt kan det sies at slagseigheten øker med tiltagende konsentrasjon av polyetylheksylakrylat mens derimot gjennomsiktigheten avtar med (3.5 times the polymer concentration of 2-ethylhexyl acrylate in weight percent). When you are in the specified range, polymers are obtained which are not only distinguished by good shear strength, but also by transparency. In general, it can be said that impact strength increases with increasing concentration of polyethylhexyl acrylate, while, on the other hand, transparency decreases with
v stigende partikkelstørrelse. v increasing particle size.
For en konsentrasjon på 9 vektprosent poly-2-etylheksylakrylat i polymerisatet av vinylklorid er det følgelig vanlig med en maksimal midlere diameter av poly-2-etylheksylakrylat-partiklene på 94 nya, fortrinnsvis av 44 mu, og en minimal midlere diameter på 1,5 mu. For en konsentrasjon på 5,5 vektprosent .blir det folgende verdier: midlere diameter maksimum 178 ima, fortrinnsvis Consequently, for a concentration of 9% by weight of poly-2-ethylhexyl acrylate in the vinyl chloride polymer, a maximum average diameter of the poly-2-ethylhexyl acrylate particles of 94 nya, preferably of 44 mu, and a minimum average diameter of 1.5 mu. For a concentration of 5.5% by weight, the following values are obtained: mean diameter maximum 178 ima, preferably
.128 mu, minimum midlere diameter 14 nju. .128 mu, minimum mean diameter 14 nju.
1 diagrammet på fig. 1 vises gyldighetsområdet for oppfinnelsen 1 the diagram in fig. 1 shows the scope of the invention
fremstilt ved. flateinnholdet av ABCD. Den skraverte flate utgjor et mer foretrukket gyldighetsområde. produced by. the surface area of ABCD. The shaded area constitutes a more preferred range of validity.
Fortrinnsvis blir det anvendt et polymerisat av 2-etylheksylakrylat, som inneholder mer enn 90 vektprosent 2-etylheksylakrylat. Preferably, a polymer of 2-ethylhexyl acrylate is used, which contains more than 90% by weight of 2-ethylhexyl acrylate.
Som komonomere kan det anvendes lavere akrylat, eksempelvis metyl-, etyl-, propyl, isopropyl, butyl-, Lsobutyl- og heksyl-akrylat. Lower acrylate can be used as comonomers, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl and hexyl acrylate.
For anvendelse av fremgangsmåten i folge oppfinnelsen blir det tatt polymerisater av 2-etylheksylakrylat med gitte og kjente midlere partikkeldlametre. Disse polymerisater blir fortrinnsvis anvendt i form av vandige dispersjoner. De kan fremstilles ved emulsjonspolymerisasjon av 2-etylheksylakrylat, eventuelt sammen med lavere akrylat som komonomere, i nærvær av vannloselige initiatorer og emulgatorer. Den midlere partikkeldiameter av de dannede polymerer av 2-etylheksylakrylat blir bestemt ved betingelsene for emuLsjonspolymerisasjonen etter kjent metode. For the application of the method according to the invention, polymers of 2-ethylhexyl acrylate with given and known mean particle diameters are taken. These polymers are preferably used in the form of aqueous dispersions. They can be produced by emulsion polymerization of 2-ethylhexyl acrylate, optionally together with lower acrylate as comonomers, in the presence of water-soluble initiators and emulsifiers. The average particle diameter of the formed polymers of 2-ethylhexyl acrylate is determined by the conditions of the emulsion polymerization according to a known method.
Polyakrylatdispersjoner med forskjellig partikkeldiameter kan f.eks. fremstilles ved variasjon av den benyttede emulgatormengde. Som emulgatorer benyttes hovedsakelig salter av fettsyrer med Polyacrylate dispersions with different particle diameters can e.g. produced by varying the amount of emulsifier used. Salts of fatty acids are mainly used as emulsifiers
en kjedelengde fra 12 til 18 karbonatomer. Fortrinnsvis blir alkali- eller ammoniumsaltet av laurinsyre, myristinsyre, olje-syre, kokosfettsyre, palmitinsyre, stearinsyre bl.a. anvendt. Disse emulgatorer blir hensiktsmessig anvendt i mengder fra 2 til 12 vektprosent, beregnet på monomert akrylat. Blir f.eks. a chain length of 12 to 18 carbon atoms. Preferably, the alkali or ammonium salt of lauric acid, myristic acid, oleic acid, coconut fatty acid, palmitic acid, stearic acid i.a. used. These emulsifiers are suitably used in amounts from 2 to 12 percent by weight, calculated on monomeric acrylate. Will e.g.
emulsjonspolymerisasjonen av 2-etylheksylakrylat gjennomfort i nærvær av 2 vektprosent natriumlaurat som emulgator så utgjor den midlere partikkeldiameter av polyakrylatet ca. 139 nya. The emulsion polymerization of 2-ethylhexyl acrylate is carried out in the presence of 2% by weight of sodium laurate as an emulsifier, so the average particle diameter of the polyacrylate is approx. 139 new.
Blir det derimot benyttet 6 vektprosent natriumlaurat blir If, on the other hand, 6% by weight of sodium laurate is used,
den midlere partikkeldiameter på ca. 47 mp. the average particle diameter of approx. 47 mp.
En videre mulighet for å influere på partikkeldiameteren av polymerisatet av 2-etylheksylakrylat består i tilsetningsmåten for monomerakrylat og/eller emulgator. Hvis man f.eks. tilforer 3 vektprosent natriumlaurat ved polymerisasjonens begynnelse og tilforer deretter 3 vektprosent i lopet av reaksjonen så utgjor den midlere partikkeldiameter ca. 72 nya, i stedet for 47 mu ved tilsetning av hele emulgatormengden samtidig. A further possibility of influencing the particle diameter of the polymerizate of 2-ethylhexyl acrylate consists in the method of addition of monomer acrylate and/or emulsifier. If you e.g. adds 3% by weight of sodium laurate at the beginning of the polymerization and then adds 3% by weight during the course of the reaction, so the mean particle diameter is approx. 72 new, instead of 47 mu when adding the entire amount of emulsifier at the same time.
Når det onskes polyakrylatdispersjoner med storre midlere partikkeldiameter kan polymerisasjonen av det monomere '2-etylheksylakrylat gjennomfores i nærvær av et forutdannet lateks av polyakrylat. I dette tilfelle blir polymerisasjonsbetingelsene valgt slik at utelukkende de tilsatte polymer i sa tpar tikl er vokser videre uten dannelse av nye partikler. When polyacrylate dispersions with a larger average particle diameter are desired, the polymerization of the monomeric 2-ethylhexyl acrylate can be carried out in the presence of a preformed latex of polyacrylate. In this case, the polymerization conditions are chosen so that only the added polymer in the particle grows further without the formation of new particles.
Den midlere partikkeldiameter kan bestemmes ved hjelp av for-skjellige metoder, f.eks. ved lysspredningsmåling, ved hjelp av skivesentrifuge eller ved elektronmikroskopi. I det siste tilfelle loper man den risiko at polymerpartiklene ved frem-stillingen av provene og/eller ved målingene kan bli så mye for-andret på grunn av den lave mykningstemperaturen, ved agglomerering eller smelting, at det ikke er mulig å gjennomfore en tilfreds-stillende bestemmelse. The average particle diameter can be determined using different methods, e.g. by light scattering measurement, by means of a disk centrifuge or by electron microscopy. In the latter case, one runs the risk that the polymer particles during the preparation of the sample and/or during the measurements may be so much changed due to the low softening temperature, by agglomeration or melting, that it is not possible to carry out a satisfactory stipulation.
Såpetitreringen har på grunn av sin enkelhet vist seg særlig Due to its simplicity, the soap titration has proven itself in particular
egnet. Denne metode er kjent og blir anvendt av flere forskere (Houben-Weyl XIV/1, side 369). Disse berorer også bestemmelsen for spesifikk partikkeloverflate av undersbkte dispersjoner. Betegner d den midlere partikkeldiameter i mu og E den emulgatormengde som må til for å dekke et gram av polymerisatet med et monomolekylart emulgatorskikt, og antar man densiteten av polyakrylatet til en verdi av 1,00 så får man etter Jacobi, Angew, Chem. 64, 539 - 543 suitable. This method is known and is used by several researchers (Houben-Weyl XIV/1, page 369). These also depend on the determination of the specific particle surface area of investigated dispersions. If d denotes the mean particle diameter in mu and E the amount of emulsifier needed to cover one gram of the polymer with a monomolecular emulsifier layer, and if the density of the polyacrylate is assumed to be 1.00, then according to Jacobi, Angew, Chem. 64, 539 - 543
(1952) folgende ligning (1952) following equation
for titreringen med "Mersolat K 30". for the titration with "Mersolat K 30".
Polymerisasjonen av vinylklorid gjennomføres i vandig emulsjon. The polymerization of vinyl chloride is carried out in an aqueous emulsion.
Som emulgatorer benyttes hovedsakelig salter av fettsyrer med Salts of fatty acids are mainly used as emulsifiers
en kjedelengde fra 12 - 18 karbonatomer. Fortrinnsvis benyttes alkali- eller ammoniumsalter.av laurinsyre, myristinsyre, olje-syre, kokosfettsyre, palmitinsyre, stearinsyre og lignende. Disse emulgatorer blir fortrinnsvis anvendt i mengder fra 0,05 til 1% (beregnet på vekten av vinylklorid). a chain length from 12 - 18 carbon atoms. Alkali or ammonium salts of lauric acid, myristic acid, oleic acid, coconut fatty acid, palmitic acid, stearic acid and the like are preferably used. These emulsifiers are preferably used in amounts from 0.05 to 1% (calculated on the weight of vinyl chloride).
Som,.katalysatorer blir det benyttet vannloselige radikaldannere, som peroksyd, persulfat, azoforbindelser, redoksforbindelser. Mengden ligger fortrinnsvis ved 0,05 til 0,5 vektprosent beregnet på vinylklorid^As catalysts, water-soluble radical generators are used, such as peroxide, persulphate, azo compounds, redox compounds. The amount is preferably 0.05 to 0.5% by weight calculated on vinyl chloride^
Polymerisasjonen kan gjennomfores i nærvær av polymerisasjons-regulatorer. Som polymerisasjons-regulator anvendes merkaptan og mettede eller umettede halogen-hydrokarbonforbindelser. Mengden av anvendt regulator avhenger av arten av disse og de innstilte K-verdier. Eksempelvis blir dodecylmerkaptan anvendt i mengder fra 0,01 til 0,2 vektprosent, beregnet på vinylklorid. Trikloretylen eller 1 >2-dikloretylen eller bromoform blir anvendt i mengder fra 0,1 til 5%. Fortrinnsvis skal K-verdiene av de oppnådde vinylkloridpolymerisater utgjore fra 60 til 75. The polymerization can be carried out in the presence of polymerization regulators. Mercaptan and saturated or unsaturated halogen-hydrocarbon compounds are used as polymerization regulators. The amount of regulator used depends on the nature of these and the set K values. For example, dodecyl mercaptan is used in amounts from 0.01 to 0.2 percent by weight, calculated on vinyl chloride. Trichlorethylene or 1>2-dichloroethylene or bromoform are used in amounts from 0.1 to 5%. Preferably, the K values of the obtained vinyl chloride polymers should be from 60 to 75.
Polymerisas jonen gjennomfores slik at den vandige dispersjon av 2-etylheksylakrylat-polymerisat blandes sammen med katalysator, emulgator og eventuelt regulator i en trykk-kjele, som gjor det mulig å oppnå en god blanding, f.eks. et trykkar utstyrt med roreverk, og at det monomeré vinylklorid i det minste tilfores i en slik mengde at man når metningstrykket for vinylklorid ved gitt reaksj onstemperatur. The polymerization is carried out so that the aqueous dispersion of 2-ethylhexyl acrylate polymer is mixed together with catalyst, emulsifier and possibly regulator in a pressure boiler, which makes it possible to achieve a good mixture, e.g. a pressure vessel equipped with an agitator, and that the monomeric vinyl chloride is at least supplied in such an amount that the saturation pressure for vinyl chloride is reached at a given reaction temperature.
Etter avsluttet polymerisasjon blir polymerisatet bearbeidet etter kjent metode, f.eks. ved koagulering under tilsetning av elektrolytter, utskillelse fra polymerisasjons-serum ved utslyngning, vasket og torket i en torketrommel, eller ved forstovnings-torking eller ved spruting på en valseterker. After completion of polymerization, the polymer is processed according to a known method, e.g. by coagulation during addition of electrolytes, separation from polymerization serum by ejection, washed and dried in a drying drum, or by atomization drying or by spraying on a roller drier.
I fig. 2 og 3 er gjennomsiktigheten (uttrykt som uklarhet) henholdsvis snittslagseigheten angitt som funksjon av den midlere partikkeldiameter av polyakrylat for polymerisat av vinylklorid med forskjellig innhold i polymeren av,2-etylheksylakrylat, • nemlig 4%, 5,5%, 7,5% og 9%. Som det fremgår av skissen viser kurvene for snittslagseighet et maksimum, kurvene for gjennomsiktigheten er derimot rette linjer, hvis stigning avhenger av innholdet av polyakrylat i polymerisatet av vinylklorid. In fig. 2 and 3, the transparency (expressed as opacity) and the shear strength respectively are indicated as a function of the average particle diameter of polyacrylate for polymerizate of vinyl chloride with different contents of ,2-ethylhexyl acrylate in the polymer, namely 4%, 5.5%, 7.5% and 9%. As can be seen from the sketch, the curves for shear layer strength show a maximum, the curves for transparency, on the other hand, are straight lines, the slope of which depends on the content of polyacrylate in the vinyl chloride polymer.
Gyldighetsområdet for oppfinnelsen .er begrenset gjennom en maksimal midlere partikkeldiameter og en minimal midlere partikkeldiameter, som ovenfor er definert med hensyn til innholdet av polyakrylat i polymerisatet av vinylklorid. Det tilsvarende polymerisat av vinylklorid oppviser en forbedret slagseighet og spesielt i det foretrukne område, samtidig en god gjennomsiktighet. Ved anvendelse av polyakrylater med midlere partikkeldiameter under den angitte minimumsgrense oppnås en hoyere gjennomsiktighet, men slagseigheten skiller seg ikke nå vesentlig fra lignende umodifiserte polyvinylklorider. The scope of the invention is limited by a maximum mean particle diameter and a minimum mean particle diameter, which is defined above with regard to the content of polyacrylate in the polymerized vinyl chloride. The corresponding vinyl chloride polymer exhibits an improved impact strength and, especially in the preferred range, at the same time a good transparency. When using polyacrylates with an average particle diameter below the specified minimum limit, a higher transparency is achieved, but the impact strength does not differ significantly from similar unmodified polyvinyl chlorides.
Eksempel Example
1) I en roreautoklav av rustfritt stål med volum 12 liter innfores 6000 g saltfritt vann, 120 g laurinsyre, 60 ml 10N natriumhydroksydlosning og 5 g kaliumperoksyddisulfat og under omroring oppvarmes til 55°C. Autoklaven evakueres og spyles flere ganger ved innpresning av oksygenfritt nitrogen og evakueres,, tilslutt innpresses nitrogen til et trykk på 2 atmosfærer. 1) 6000 g of salt-free water, 120 g of lauric acid, 60 ml of 10N sodium hydroxide solution and 5 g of potassium peroxide disulphate are introduced into a stainless steel stirring autoclave with a volume of 12 liters and heated to 55°C while stirring. The autoclave is evacuated and flushed several times by forcing in oxygen-free nitrogen and evacuated, finally nitrogen is forced in to a pressure of 2 atmospheres.
Ved en autoklavtemperatur på 55°C pumpes det inn 100 g 2-etylheksylakrylat i lbpet av 2 min. og etter 10 min pumpes det inn 900 g 2-etylheksylakrylat kontinuerlig i lopet av 100 min. Etter en total reaksjonsvarighet på 4 timer ble autoklav-innholdet trykkavlastet og avkjolt. Man oppnår en tyntflytende dispersjon med et faststoff innhold på ca. 14%. Den midlere partikkeldiamter bestemmes ved såpe-titrering til 25 mp. At an autoclave temperature of 55°C, 100 g of 2-ethylhexyl acrylate is pumped in over 2 min. and after 10 minutes, 900 g of 2-ethylhexyl acrylate is pumped in continuously over the course of 100 minutes. After a total reaction duration of 4 hours, the autoclave contents were depressurized and cooled. A thin-flowing dispersion is obtained with a solids content of approx. 14%. The mean particle diameter is determined by soap titration to 25 mp.
I en roreautoklav av rustfritt stål med volum 12 liter innfores, 5400 g avsaltet vann, 700 g av den ovenfor nevnte dispersjon, som inneholder ca. 100 g poly-2-etylheksylakrylat, og 4 g kaliumperoksyddisulfat og under omrpring oppvarmes til 59°C. Autoklaven evakueres og spyles ved gjentatte innpresninger av vinylklorid og trykkavlastninger. 1900 g vinylklorid ble til-fort, trykket utgjorde da 9,1 atmosfære ved en polymerisasjons-temperatur _på 95°C. Etter ca. llj time utgjorde omsetningen ca. 75%, trykket begynte deretter å falle. Man lot trykket falle til ca. 4 atmosfærer, slapp ut det uomsatte vinylklorid og avkjblte. Dispersjonen inneholdt ca. 24% faststoff. Polymerisatet ble på vanlag måte isolert' ved koagulering med elektrolytter. 5400 g of desalted water, 700 g of the above-mentioned dispersion, which contains approx. 100 g of poly-2-ethylhexyl acrylate, and 4 g of potassium peroxide disulphate and, with stirring, are heated to 59°C. The autoclave is evacuated and flushed by repeated injection of vinyl chloride and pressure relief. 1900 g of vinyl chloride were added, the pressure then amounted to 9.1 atmospheres at a polymerization temperature of 95°C. After approx. llj hour, the turnover amounted to approx. 75%, the pressure then started to drop. The pressure was allowed to drop to approx. 4 atmospheres, released the unreacted vinyl chloride and cooled. The dispersion contained approx. 24% solids. The polymer was isolated in the usual way by coagulation with electrolytes.
To ytterligere polymerisater av vinylklorid ble fremstilt på lignende måte, men med den forskjell at den innforte mengde poly-2-etylheksylakrylat utgjorde 140 g, henholdsvis 170 g og vinyl-kloridmengden tilsvarte 1860 g og 1830 g. Two further polymers of vinyl chloride were prepared in a similar manner, but with the difference that the amount of poly-2-ethylhexyl acrylate introduced was 140 g and 170 g, respectively, and the amount of vinyl chloride corresponded to 1860 g and 1830 g.
Ved valseblanding av blandinger av 60,5 vektdeler vinylklorid-polymerisat, 1 vektdel organisk tiotinnstabilisator og 1 vektdel glidemiddel i lopet av 10 min. ved 180°C på en blande-valse-apparatur og presser som også holdes ved 180°C ble det bearbeidet plater av tykkelse 1 mm og 4 mm. Snittslagseigheten av små-norm-staver ble bestemt etter DIN 53453. Uklarheten ble målt ved hjelp av "Haze"-instrumenter fra firma Evans Electroselenium Ltd. i Halstead (England) etter ASTM D 1003-61. Betegnelsen for "Haze" eller "uklarhet" er forholdet mellom gjennomgang av lys gjennom en prove Td og uforstyrret gjennomfallende lys Tt. Verdien gis i %. By roller mixing mixtures of 60.5 parts by weight of vinyl chloride polymer, 1 part by weight of organic thiotin stabilizer and 1 part by weight of lubricant in the course of 10 min. at 180°C on a mixing-roller apparatus and presses which are also kept at 180°C, sheets of thickness 1 mm and 4 mm were processed. The average impact strength of small-norm rods was determined according to DIN 53453. The haze was measured using "Haze" instruments from the company Evans Electroselenium Ltd. in Halstead (England) according to ASTM D 1003-61. The designation for "Haze" or "turbidity" is the ratio between the passage of light through a sample Td and undisturbed transmitted light Tt. The value is given in %.
Resultatet er angitt i tabell 1. 2) En dispersjon av poly-2-etylheksylakrylat fremstilles som i eksempel 1, men ved anvendelse av bare 60 g laurinsyre og 30 ml natriumhydroksydlosning i stedet for 120 g henholdsvis 60 ml. Den bestemte, ved såpetitrering, midlere partikkeldiameter utgjorde 43 mp. The result is shown in table 1. 2) A dispersion of poly-2-ethylhexyl acrylate is prepared as in example 1, but using only 60 g of lauric acid and 30 ml of sodium hydroxide solution instead of 120 g and 60 ml, respectively. The average particle diameter determined by soap titration was 43 mp.
Fire vinylkloridpolymerisater ble fremstilt under anvendelse av 60, henholdsvis 100, 140 eller 170 g poly-2-etylheksylakrylat i form av den ovenfor nevnte dispersjon, på samme måte som i eksempel 1, bearbeidet til plater og testet. Verdiene er gjen-gitt i tabell 2. 3) En dispersjon av poly-2-etylheksylakrylat ble fremstilt som angitt i eksempel 1, men under anvendelse av bare 30 g laurinsyre og 15 ml natriumhydroksydlosning i stedet for 120 g, henholdsvis 60 ml. Ved såpetitrering ble den midlere partikkeldiameter bestemt til 74 mu. Four vinyl chloride polymers were prepared using 60, respectively 100, 140 or 170 g of poly-2-ethylhexyl acrylate in the form of the above-mentioned dispersion, in the same way as in example 1, processed into plates and tested. The values are reproduced in table 2. 3) A dispersion of poly-2-ethylhexyl acrylate was prepared as indicated in example 1, but using only 30 g of lauric acid and 15 ml of sodium hydroxide solution instead of 120 g, respectively 60 ml. By soap titration, the average particle diameter was determined to be 74 µm.
Fire vinylkloridpolymsrisater ble fremstilt under anvendelse av 60, henholdsvis 100, 140 eller 170 g poly-2-etylheksylakrylat i form av den ovenfor nevnte dispersjon, som i eksempel 1, bearbeidet til- plater og provet. Four vinyl chloride polymer resins were prepared using 60, respectively 100, 140 or 170 g of poly-2-ethylhexyl acrylate in the form of the above-mentioned dispersion, as in example 1, processed into plates and tested.
De oppnådde måleverdiene er angitt i tabell 3. The measured values obtained are indicated in table 3.
4) I en roreautoklav av rustfritt stål med volum 12 liter innfores 6000 g avsaltet vann, 20 g laurinsyre, 10 ml 10N natriumhydroksydlosning og 1000 g 2-etylheksylakrylat og autoklaven oppvarmes under omroring til 55°C. Autoklaven evakueres og spyles ved gjentatte innpresninger av oksygenfri nitrogen og evakueres., tilslutt innpresses nitrogen til trykket utgjor 2 atmosfærer. 4) 6000 g of desalted water, 20 g of lauric acid, 10 ml of 10N sodium hydroxide solution and 1000 g of 2-ethylhexyl acrylate are introduced into a stainless steel stirring autoclave with a volume of 12 litres, and the autoclave is heated while stirring to 55°C. The autoclave is evacuated and flushed by repeated injection of oxygen-free nitrogen and evacuated, finally nitrogen is injected until the pressure reaches 2 atmospheres.
Ved en autoklav-temperatur på 55°C innfores 5 g kaliumperoksyddisulfat som losning i 60 ml saltfritt vann. Etter 4 timer blir autoklavinnholdet trykkavlastet og avkjolt. Man oppnår en tyntflytende dispersjon med et faststoffinnhold fra ca. 14% og ved såpetitrering bestemmes den midlere partikkeldiameter på 13 9 mu. At an autoclave temperature of 55°C, 5 g of potassium peroxide disulphate are introduced as a solution in 60 ml of salt-free water. After 4 hours, the autoclave contents are depressurized and cooled. A thin-flowing dispersion is obtained with a solids content of approx. 14% and by soap titration, the average particle diameter of 13 9 mu is determined.
Fire vinylkloridpolymerisater ble fremstilt under anvendelse av 60, henholdsvis 100, 140 eller 170 g.-poly-2-etylheksylakrylat i. form av den ovenfor nevnte dispersjon, som i eksempel 1, bearbeidet til plater og provet. Four vinyl chloride polymers were prepared using 60, respectively 100, 140 or 170 g of poly-2-ethylhexyl acrylate in the form of the above-mentioned dispersion, as in example 1, processed into plates and tested.
De målte verdier er oppgitt i tabell 4. The measured values are given in table 4.
Forsokene 1 til 3 (eksempel 1), 4 til 7 (eksempel 2), 8 til 10 (eksempel 3) og 12 (eksempel 4) ligger innenfor rammen av det foretrukne område for oppfinnelsen. Polymerisatene er gjennom-siktige og slagfaste. Experiments 1 to 3 (Example 1), 4 to 7 (Example 2), 8 to 10 (Example 3) and 12 (Example 4) are within the scope of the preferred scope of the invention. The polymers are transparent and impact resistant.
Ved forsokene 11 (eksempel 3) og 13 og 14 (eksempel 4), som ligger innenfor den generelle rammen for oppfinnelsen, oppviser polymerisatene en meget hoy snittslagseighet. In tests 11 (Example 3) and 13 and 14 (Example 4), which lie within the general scope of the invention, the polymers show a very high shear strength.
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1074370A CH528553A (en) | 1970-07-15 | 1970-07-15 | Vinyl chloride polymers - with high transparency and impact resistance by graft polymerising vinyl chloride onto 2-eth |
| CH1836970A CH573460A5 (en) | 1970-12-11 | 1970-12-11 | Vinyl chloride polymers - with high transparency and impact resistance by graft polymerising vinyl chloride onto 2-eth |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO138064B true NO138064B (en) | 1978-03-13 |
| NO138064C NO138064C (en) | 1978-06-21 |
Family
ID=25707198
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO2682/71A NO138064C (en) | 1970-07-15 | 1971-07-13 | PROCEDURE FOR THE PRODUCTION OF IMPACT-RESISTANT, WEATHER-RESISTANT POLYMERIZATES OF VINYL CHLORIDE |
Country Status (20)
| Country | Link |
|---|---|
| US (1) | US3776982A (en) |
| JP (1) | JPS5419434B1 (en) |
| AT (1) | AT320967B (en) |
| AU (1) | AU453057B2 (en) |
| BE (1) | BE770011A (en) |
| BR (1) | BR7104446D0 (en) |
| CA (1) | CA945281A (en) |
| CS (1) | CS171707B2 (en) |
| DE (1) | DE2103438C2 (en) |
| DK (1) | DK133814B (en) |
| ES (1) | ES393179A1 (en) |
| FR (1) | FR2101667A5 (en) |
| GB (1) | GB1302639A (en) |
| IL (1) | IL37319A (en) |
| NL (1) | NL7109787A (en) |
| NO (1) | NO138064C (en) |
| PL (1) | PL80629B1 (en) |
| RO (1) | RO62190A (en) |
| SE (1) | SE384868B (en) |
| SU (1) | SU420184A3 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3969431A (en) * | 1971-09-20 | 1976-07-13 | Stauffer Chemical Company | Reinforcement of vinyl chloride resins with suspension emulsion interpolymers |
| CH566354A5 (en) * | 1972-06-08 | 1975-09-15 | Lonza Ag | |
| CH586722A5 (en) * | 1973-12-07 | 1977-04-15 | Lonza Ag | |
| US4162239A (en) * | 1974-11-14 | 1979-07-24 | Lonza Ltd. | Process for the production of transparent polymers of vinyl chloride with very high impact strength |
| DE3216989A1 (en) * | 1982-05-06 | 1983-11-10 | Chemische Werke Hüls AG, 4370 Marl | HIGHLY TRANSPARENT IMPACT TOOLS BASED ON POLYVINYL CHLORIDE |
| DE3316224A1 (en) * | 1983-05-04 | 1984-11-08 | Chemische Werke Hüls AG, 4370 Marl | TRANSPARENT IMPACT TOOLS BASED ON POLYVINYL CHLORIDE |
| DE4330180C2 (en) * | 1993-08-31 | 1998-02-19 | Buna Sow Leuna Olefinverb Gmbh | Process for the preparation of impact-resistant graft copolymers of vinyl chloride |
| FR3120018B1 (en) | 2021-02-22 | 2023-09-29 | Psa Automobiles Sa | Aerator for motor vehicles equipped with a dual-control adjustment wheel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2686172A (en) * | 1951-05-22 | 1954-08-10 | Goodrich Co B F | Tough, strong, and easily processed vinyl chloride interpolymers containing free side-chain hydroxyl groups |
| DE1090857B (en) * | 1958-12-13 | 1960-10-13 | Basf Ag | Process for the production of impact-resistant vinyl chloride polymers |
| DE1132725B (en) * | 1959-11-18 | 1962-07-05 | Hoechst Ag | Process for the production of copolymers with an extremely heterogeneous structure |
| GB1064848A (en) * | 1962-11-17 | 1967-04-12 | Kureha Chemical Ind Co Ltd | Method for the production of vinyl resins |
| FR1386610A (en) * | 1964-01-17 | 1965-01-22 | Solvay | Stable resinous compositions based on vinyl polymers |
| DE1227656C2 (en) * | 1964-06-20 | 1973-09-20 | PROCESS FOR THE PREPARATION OF MIXED POLYMERIZATES OF VINYL CHLORIDE |
-
1971
- 1971-01-26 DE DE2103438A patent/DE2103438C2/en not_active Expired
- 1971-02-14 BR BR4446/71*A patent/BR7104446D0/en unknown
- 1971-07-12 SE SE7109000A patent/SE384868B/en unknown
- 1971-07-12 ES ES393179A patent/ES393179A1/en not_active Expired
- 1971-07-12 CA CA117,922A patent/CA945281A/en not_active Expired
- 1971-07-13 NO NO2682/71A patent/NO138064C/en unknown
- 1971-07-13 DK DK346471AA patent/DK133814B/en unknown
- 1971-07-13 FR FR7125700A patent/FR2101667A5/fr not_active Expired
- 1971-07-13 CS CS5140A patent/CS171707B2/cs unknown
- 1971-07-13 RO RO67646A patent/RO62190A/ro unknown
- 1971-07-14 BE BE770011A patent/BE770011A/en unknown
- 1971-07-14 GB GB3307671A patent/GB1302639A/en not_active Expired
- 1971-07-14 IL IL37319A patent/IL37319A/en unknown
- 1971-07-14 US US00162346A patent/US3776982A/en not_active Expired - Lifetime
- 1971-07-14 AT AT614671A patent/AT320967B/en not_active IP Right Cessation
- 1971-07-14 AU AU31226/71A patent/AU453057B2/en not_active Expired
- 1971-07-14 PL PL1971149448A patent/PL80629B1/en unknown
- 1971-07-15 JP JP5219871A patent/JPS5419434B1/ja active Pending
- 1971-07-15 NL NL7109787A patent/NL7109787A/xx not_active Application Discontinuation
- 1971-07-15 SU SU1683576A patent/SU420184A3/en active
Also Published As
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| IL37319A0 (en) | 1971-10-20 |
| CS171707B2 (en) | 1976-10-29 |
| AU453057B2 (en) | 1974-09-19 |
| ES393179A1 (en) | 1974-06-01 |
| NL7109787A (en) | 1972-01-18 |
| BE770011A (en) | 1972-01-14 |
| GB1302639A (en) | 1973-01-10 |
| DE2103438A1 (en) | 1972-01-27 |
| US3776982A (en) | 1973-12-04 |
| NO138064C (en) | 1978-06-21 |
| BR7104446D0 (en) | 1973-03-08 |
| IL37319A (en) | 1974-11-29 |
| DE2103438C2 (en) | 1981-11-26 |
| SE384868B (en) | 1976-05-24 |
| FR2101667A5 (en) | 1972-03-31 |
| JPS5419434B1 (en) | 1979-07-14 |
| AT320967B (en) | 1975-03-10 |
| PL80629B1 (en) | 1975-08-30 |
| CA945281A (en) | 1974-04-09 |
| AU3122671A (en) | 1973-01-18 |
| DK133814B (en) | 1976-07-26 |
| SU420184A3 (en) | 1974-03-15 |
| RO62190A (en) | 1977-06-15 |
| DK133814C (en) | 1976-12-20 |
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